CN109755038A - The preparation method and application of flexible all-solid-state supercapacitor based on two-dimensional drape metalloporphyrin frame ultrathin nanometer piece - Google Patents
The preparation method and application of flexible all-solid-state supercapacitor based on two-dimensional drape metalloporphyrin frame ultrathin nanometer piece Download PDFInfo
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Abstract
The invention discloses a kind of preparation method and applications of flexible all-solid-state supercapacitor based on two-dimensional drape metalloporphyrin frame ultrathin nanometer piece, specifically include six steps, are respectively as follows: the preparation of one, two-dimensional drape Cu-TCPP ultrathin nanometer piece；Two, the preparation of Cu-TCPP film；Three, the preparation of PPy film；Four, the preparation of Cu-TCPP/PPy flexible composite film；Five, H2SO4The preparation of-PVA hydrogel；Six, the preparation of Cu-TCPP/PPy flexibility all-solid-state supercapacitor.Two-dimensional ultrathin Cu-TCPP nanometer sheet using method disclosed by the invention preparation has pleated structure, provides the duct of larger size, is easy to electrolyte ion transmission；The flexible all-solid-state supercapacitor prepared on this basis has excellent electrochemical energy storage performance and good mechanical performance, remains to holding capacitor under wide-angle bending and stablizes.
Description
Technical field
The present invention relates to capacitance technology fields, are specifically related to a kind of based on two-dimensional drape metalloporphyrin frame ultrathin nanometer
The preparation method of the flexible all-solid-state supercapacitor of piece and its application in electrochemical energy storage field.
Background technique
With the development of Portable flexible electronic equipment, novel electron equipment is gradually to micromation, intelligence, flexibility, super
Long standby direction is developed, and people produce great interest to flexible products such as flexible mobile phone, wearable electronics,
Also to transparent flexible electronics device, more stringent requirements are proposed for this, it is desirable that the memory device for providing energy for electronic product has
Gently, the features such as thin, soft.But lithium ion battery and the business energy storage device of supercapacitor are usually too heavy and without flexibility,
It is difficult to meet the particular/special requirement of flexible portable electronic equipment.Currently, flexible super capacitor is because having high power density, fast
Performance advantages and light, thin, the soft structural advantages such as the fast cycle life of charge/discharge rates and overlength, are widely used as soft
The electrochemical energy storage device of property electronic device, the highest attention by academia and industrial circle.
Two-dimensional metallic organic frame (MOFs) is the one kind formed by metal ion and organic ligand by being coordinated key connection
Two-dimensional material has many advantages, such as biggish specific surface area, reactivity site abundant, adjustable cellular structure.Numerous
In MOFs material, two-dimensional metallic porphyrin frame (MPFs) is because having biggish porosity, a large amount of pi-conjugated stacking, quickly electricity
Lotus transmission, reactivity site abundant and structural stability are widely used in electrochemical energy storage field, particularly, pi-conjugated
The conjugated molecule structure of stacking is conducive to improve electronic conductivity, is widely used in flexible energy storage field.But MPFs is low
Conductivity limits it in the application of flexible energy storage device.
Polypyrrole in flexible energy storage field there is great advantage still to pass through because of its intrinsic flexibility and electric conductivity
PPy fexible film prepared by electrochemical polymerization mode has fine and close structure, hinders electrolyte ion in PPy membrane electrode
Interior high efficiency of transmission, and then limit further increasing for its capacitive property.
More some researches show that, composite material can raise each growing for material and keep away that its is short, be conducive to improve by " synergistic effect "
The synthesis energy storage property of material.
Summary of the invention
It is an object of the invention to solve deficiency in the prior art, provide a kind of based on two-dimensional drape metalloporphyrin frame
(Cu-TCPP) ultrathin nanometer piece constructs Cu-TCPP/PPy combination electrode, and assembles the preparation side of flexible all-solid-state supercapacitor
Method；The flexible all-solid-state supercapacitor prepared has excellent electrochemical energy storage performance and good mechanical performance.
The technical solution of the present invention is as follows: the flexibility based on two-dimensional drape metalloporphyrin frame ultrathin nanometer piece is all solid state super
The preparation method of capacitor, specific preparation step are as follows:
Step 1: the preparation of two-dimensional drape Cu-TCPP ultrathin nanometer piece
1) by Gerhardite (Cu (NO3)2·3H2O), 4,4 '-bipyridyls (BPY), polyvinylpyrrolidone (PVP)
It is dissolved in the in the mixed solvent of n,N-Dimethylformamide (DMF) and ethyl alcohol (V:V=3:1), ultrasonic (power 240W, frequency
40kHz) 5min, until forming uniform solution, the addition of column-supporting agent BPY is mainly used for regulating and controlling spacing between layers；
2) by 5,10,15,20- tetracarboxylic phenyl copper porphyrin pheno (H6TCPP) it is dissolved in the mixed of DMF and ethyl alcohol (V:V=3:1)
In bonding solvent, ultrasound (power 240W, frequency 40kHz) 5min forms uniform solution, is added dropwise in solution (1), surpasses
It after sound (power 240W, frequency 40kHz) 10min, is transferred in air dry oven, in 80-85 DEG C of reaction 3h, wait react knot
Beam is cooled to room temperature, by products therefrom ethanol washing, centrifugation (12000rpm, 10min) 3 times, H6The manufacturer of TCPP is
Sa Si chemical technology (Shanghai) Co., Ltd., structural formula are as follows:
Step 2: the preparation of Cu-TCPP film
Two-dimensional drape Cu-TCPP ultrathin nanometer piece is dispersed in containing iodine (I2) acetone in, under 30V potential bias,
Two-dimensional drape Cu-TCPP ultrathin nanometer piece is deposited to the surface ITO, obtains Cu-TCPP film by electrophoretic deposition 30s.
Step 3: the preparation of PPy film
Solution is prepared: paratoluenesulfonic acid sodium salt, p-methyl benzenesulfonic acid monohydrate and pyrroles being add to deionized water, stood
After 10h, magnetic agitation 10min；Using Ag/AgCl electrode as reference electrode, Pt piece is to electrode, and the ito glass of blank is work
Electrode, constant voltage 0.8V carry out electrochemical polymerization, and conduction time 600s prepares PPy fexible film.
Step 4: the preparation of Cu-TCPP/PPy flexible composite film
Solution is prepared: paratoluenesulfonic acid sodium salt, p-methyl benzenesulfonic acid monohydrate and pyrroles being add to deionized water, stood
After 10h, magnetic agitation 10min, using Ag/AgCl electrode as reference electrode, Pt piece is to electrode, and step 2 preparation covers
The ito glass of Cu-TCPP film is working electrode, and constant voltage 0.8V carries out electrochemical polymerization, conduction time 600s, system
Standby Cu-TCPP/PPy composite and flexible film out.
Step 5: H2SO4The preparation of-PVA hydrogel
Polyvinyl alcohol (PVA) is added into eggplant type bottle, ultrapure water is added and is under agitation added dropwise to the concentrated sulfuric acid
Above-mentioned solution, seals reaction flask after being added dropwise, and is transferred to 85 DEG C of oil bath pan reaction 2h, and solution becomes clear, is cooled to
Room temperature to use in step 6.
Step 6: the preparation of Cu-TCPP/PPy flexibility all-solid-state supercapacitor
2 drop H are added dropwise in Cu-TCPP/PPy composite and flexible electrode surface2SO4- PVA hydrogel will be another after standing 10min
A Cu-TCPP/PPy composite and flexible electrode is carefully covered on hydrogel surface, stands for 24 hours, sufficiently solidifies to hydrogel, obtain
Cu-TCPP/PPy flexibility all-solid-state supercapacitor.
Further, the flexible all-solid-state supercapacitor based on two-dimensional drape metalloporphyrin frame ultrathin nanometer piece
It can be applicable in electrochemical energy storage.
The invention has the benefit that
1. utilizing Cu-TCPP nanometers of two-dimensional ultrathin of method disclosed by the invention preparation compared to existing preparation method
Piece has pleated structure, provides the duct of larger size, is easy to electrolyte ion transmission；
2. the present invention prepares Cu-TCPP/PPy fexible film electricity in such a way that electrophoretic deposition-electrochemical polymerization combines
Pole, it is easy to operate, it can be completed under normal temperature and pressure conditions；The Cu-TCPP/PPy composite and flexible electrode prepared has better than single
The electrochemical energy storage property of one group of sub-electrode；
3. flexibility all-solid-state supercapacitor prepared by the present invention, has excellent electrochemical energy storage performance and good machine
Tool performance remains to holding capacitor under wide-angle bending and stablizes.
Detailed description of the invention
Fig. 1 is the TEM photo for the two-dimentional Cu-TCPP ultrathin nanometer piece that embodiment 1 obtains；
Fig. 2 is the SEM photograph for the two-dimentional Cu-TCPP ultrathin nanometer piece film that embodiment 2 obtains；
Fig. 3 is the front SEM photograph for the PPy film that embodiment 3 obtains；
Fig. 4 is the front SEM photograph for the Cu-TCPP/PPy composite and flexible electrode that embodiment 4 obtains；
Fig. 5 is the section SEM photograph for the Cu-TCPP/PPy composite and flexible electrode that embodiment 4 obtains；
Fig. 6 is the tiling figure for the Cu-TCPP/PPy composite and flexible electrode that embodiment 4 obtains；
Fig. 7 is the folding picture for the Cu-TCPP/PPy composite and flexible electrode that embodiment 4 obtains；
Fig. 8 is the Cu-TCPP/PPy composite and flexible electrode CV figure that embodiment 5 obtains；
Fig. 9 is the Cu-TCPP/PPy composite and flexible electrode GCD figure that embodiment 6 obtains；
Figure 10 is the tiling figure for the Cu-TCPP/PPy flexibility all-solid-state supercapacitor that embodiment 7 obtains；
Figure 11 is the folding picture for the Cu-TCPP/PPy flexibility all-solid-state supercapacitor that embodiment 7 obtains；
Figure 12 is the Cu-TCPP/PPy flexibility all-solid-state supercapacitor CV figure that embodiment 8 obtains；
Figure 13 is the Cu-TCPP/PPy flexibility all-solid-state supercapacitor GCD figure that embodiment 9 obtains；
Figure 14 is the obtained Cu-TCPP/PPy flexibility all-solid-state supercapacitor of embodiment 10 under different bending angles
Capacity retention figure.
Specific embodiment
Following embodiment further illustrates the contents of the present invention, but should not be construed as limiting the invention.Without departing substantially from
In the case where essence of the present invention, to modification made by the method for the present invention, step or condition and replaces, belong to model of the invention
It encloses.
Embodiment 1: the preparation of two-dimentional Cu-TCPP ultrathin nanometer piece
(1) Gerhardite (Cu (NO3)2·3H2O) (1.8mg, 0.0075mmol), 4,4'-Bipyridine (BPY)
(0.78mg, 0.005mmol), 10.0mg polyvinylpyrrolidone (PVP) are dissolved in 6mL n,N-Dimethylformamide (DMF) and second
In the mixture of alcohol (V:V=3:1)；
(2)H6TCPP (2.0mg, 0.0025mmol) is dissolved in 2mL DMF and the mixture of ethyl alcohol (V:V=3:1)；
(3) (2) are added dropwise in (1), ultrasound (power 240W, frequency 40kHz) 10min is transferred to air dry oven
In, in 80 DEG C of reaction 3h；
(4) to the end of reacting, after being cooled to room temperature removal supernatant, by products therefrom ethanol washing, centrifugation
(12000rpm, 10min) 3 times, the TEM photo of two-dimensional drape Cu-TCPP ultrathin nanometer piece, as shown in Figure 1.
The preparation of embodiment 2:Cu-TCPP film
Two-dimentional 5.0mg Cu-TCPP ultrathin nanometer piece is dispersed in containing 3mg iodine (I2) 10mL acetone in, at 30V,
Energization 30s, obtains Cu-TCPP film, the SEM photograph of two-dimensional drape Cu-TCPP ultrathin nanometer piece film, as shown in Figure 2.
The preparation of embodiment 3:PPy film
Solution is prepared: by 3.495g paratoluenesulfonic acid sodium salt, 1.141g p-methyl benzenesulfonic acid, 600 μ L pyrroles are added to 60mL and go
In ionized water, after standing 10h, magnetic agitation 10min, using Ag/AgCl electrode as reference electrode, Pt piece be to electrode, blank
Ito glass is working electrode, and constant voltage 0.8V carries out electrochemical polymerization, and conduction time 600s prepares PPy film.PPy
The front SEM photograph of film, as shown in Figure 3.
The preparation of embodiment 4:Cu-TCPP/PPy film
Solution is prepared: by 3.495g paratoluenesulfonic acid sodium salt, 1.141g p-methyl benzenesulfonic acid, 600 μ L pyrroles are added to 60mL and go
In ionized water, after standing 10h, magnetic agitation 10min, using Ag/AgCl electrode as reference electrode, Pt piece is to electrode, embodiment 2
Ito glass be working electrode, constant voltage 0.8V carries out electrochemical polymerization, and conduction time 600s prepares MPFs/PPy
Composite and flexible electrode.
The front SEM photograph of Cu-TCPP/PPy composite and flexible electrode, as shown in Figure 4；Cu-TCPP/PPy composite and flexible electricity
The section SEM photograph of pole, as shown in Figure 5；The tiling figure of Cu-TCPP/PPy composite and flexible electrode, as shown in Figure 6；Cu-TCPP/
The folding picture of PPy composite and flexible electrode, as shown in Figure 7.
The cyclic voltammetry of embodiment 5:Cu-TCPP/PPy composite and flexible electrode
Working electrode: Cu-TCPP/PPy film (original size: 1.0cm × 1.4cm；Impregnate size: 1cm × 0.7cm, matter
Amount: 0.0009g)；Reference electrode: saturated calomel electrode (SCE)；To electrode: Pt piece (1cm × 1cm)；Electrolyte: 0.5M
H2SO4；CV potential window: 0~0.5V；Film is put into electrolyte, 10min is first stood before test, in certain sweep speed
(100mV/s) activation to curve is completely coincident, and under different scanning rates, tests the CV of Cu-TCPP/PPy composite and flexible electrode
Curve, as a result as shown in Figure 8.
The constant current charge-discharge test of embodiment 6:Cu-TCPP/PPy composite and flexible electrode
Working electrode: Cu-TCPP/PPy film (original size: 1.0cm × 1.4cm；Impregnate size: 1cm × 0.7cm, matter
Amount: 0.0009g)；Reference electrode: saturated calomel electrode (SCE)；To electrode: Pt piece (1cm × 1cm)；Electrolyte: 0.5M
H2SO4；CV potential window: 0~0.5V, under different charge-discharge velocities, test Cu-TCPP/PPy composite and flexible electrode exists
GCD curve, as a result as shown in Figure 9.
The preparation of embodiment 7:Cu-TCPP/PPy composite and flexible all-solid-state supercapacitor
3g polyvinyl alcohol (PVA) is added into 100mL eggplant type bottle, 30mL ultrapure water is added, it under agitation, will
The 2.64mL concentrated sulfuric acid is added dropwise to above-mentioned solution, seals reaction flask after being added dropwise, and is transferred to 85 DEG C of oil bath pan reaction 2h, solution
Become clear, is cooled to room temperature obtained H2SO4-PVA hydrogel.
2 drop H are added dropwise in Cu-TCPP/PPy composite and flexible electrode surface2SO4-PVA hydrogel will be another after standing 10min
One Cu-TCPP/PPy composite and flexible electrode is carefully covered on hydrogel surface, stands for 24 hours, solidifies hydrogel sufficiently, with two
Piece copper foil does conductive electrode, is sealed copper foil conductive electrode and Cu-TCPP/PPy composite and flexible all-solid-state supercapacitor with adhesive tape
Dress.
The tiling figure of Cu-TCPP/PPy flexibility all-solid-state supercapacitor, as shown in Figure 10；Cu-TCPP/PPy is flexible complete
The folding picture of solid-state super capacitor, as shown in figure 11.
The cyclic voltammetry of embodiment 8:Cu-TCPP/PPy composite and flexible all-solid-state supercapacitor
Electrode will be connect with reference electrode, and be clipped in copper foil electrode side, working electrode is clipped in the copper foil electrode other side, into
The cyclic voltammetry of row Cu-TCPP/PPy composite and flexible all-solid-state supercapacitor.Cu-TCPP/PPy composite and flexible is all solid state
The CV curve of supercapacitor, as shown in figure 12.
The constant current charge-discharge test of embodiment 9:Cu-TCPP/PPy composite and flexible all-solid-state supercapacitor
Electrode will be connect with reference electrode, and be clipped in copper foil electrode side, working electrode is clipped in the copper foil electrode other side, into
The constant current charge-discharge test of row Cu-TCPP/PPy composite and flexible all-solid-state supercapacitor.Cu-TCPP/PPy composite and flexible is entirely solid
The GCD curve of state supercapacitor, as shown in figure 13.
Capacity retention of the embodiment 10:Cu-TCPP/PPy flexibility all-solid-state supercapacitor under different bending angles
Test
Electrode will be connect with reference electrode, and be clipped in copper foil electrode side, working electrode is clipped in the copper foil electrode other side, will
Flexible all-solid-state supercapacitor bending different angle carries out constant current charge-discharge test.Cu-TCPP/PPy composite and flexible is all solid state
The capacity retention of supercapacitor, as shown in figure 14.
In conjunction with Fig. 1,2 it is found that two-dimensional drape Cu-TCPP ultrathin nanometer piece between layers there are a large amount of cellular structures, this
Be conducive to the entrance of pyrroles's molecule, improve composite effect, while also increasing exchanging between composite material and electrolyte ion, electrification
It learns performance to be embodied in Figure 12,13, all-solid-state supercapacitor is when sweeping speed is 1mV/s, capacitance 148mF/cm2,
With 0.2mA/cm2Current density, the charge and discharge time reaches 370s, capacitance 65mF/cm2, this is conducive to Cu-TCPP/PPy
Composite and flexible all-solid-state supercapacitor is flexible portable power electronic equipment.
In conjunction with Fig. 6,7 it is found that Cu-TCPP/PPy composite and flexible electrode has good flexibility, repeatedly bending remains to restore former
Shape.In conjunction with Fig. 8,9 it is found that Cu-TCPP/PPy composite and flexible electrode, operation window is 0~0.5V, meets the power supply need of equipment
It asks.When sweeping speed is 1mV/s, capacitance 373mF/cm2, with 1mA/cm2Current density, the charge and discharge time reaches 350s, electricity
Capacitance is 340mF/cm2, this lays the foundation to prepare flexible all-solid-state supercapacitor.
In conjunction with Figure 14 it is found that Cu-TCPP/PPy composite and flexible all-solid-state supercapacitor is equal under different bending angles
There is higher capacity retention, mechanical performance is excellent.
Basic principles and main features and advantage of the invention have been shown and described above.But the foregoing is merely this hairs
Bright specific embodiment, technical characteristic of the invention are not limited thereto, and any those skilled in the art is not departing from this hair
The other embodiments obtained under bright technical solution should all cover within the scope of the patent of the present invention.
Claims (8)
1. a kind of preparation method of the flexible all-solid-state supercapacitor based on two-dimensional drape metalloporphyrin frame ultrathin nanometer piece,
It is characterized in that, specifically including six steps, it is respectively as follows: the preparation of one, two-dimensional drape Cu-TCPP ultrathin nanometer piece；Two, Cu-
The preparation of TCPP film；Three, the preparation of PPy film；Four, the preparation of Cu-TCPP/PPy flexible composite film；Five, H2SO4-PVA
The preparation of hydrogel；Six, the preparation of Cu-TCPP/PPy flexibility all-solid-state supercapacitor.
2. all solid state super capacitor of flexibility based on two-dimensional drape metalloporphyrin frame ultrathin nanometer piece as described in claim 1
The preparation method of device, which is characterized in that the preparation step of the two-dimensional drape Cu-TCPP ultrathin nanometer piece are as follows:
1) Gerhardite, 4,4'-Bipyridine, polyvinylpyrrolidone are dissolved in the in the mixed solvent of DMF and ethyl alcohol, ultrasound
5min, until forming uniform solution；
2) by H6TCPP is dissolved in the in the mixed solvent of DMF and ethyl alcohol, and step is added dropwise after forming uniform solution in ultrasonic 5min
It in rapid 1 solution, after ultrasonic 10min, is transferred in air dry oven, is cooled to the end of reacting in 80-85 DEG C of reaction 3h
Room temperature is centrifuged 3 times, H by products therefrom ethanol washing, under conditions of 12000rpm/10min6The structural formula of TCPP are as follows:
3. all solid state super capacitor of flexibility based on two-dimensional drape metalloporphyrin frame ultrathin nanometer piece as described in claim 1
The preparation method of device, which is characterized in that the preparation step of Cu-TCPP film are as follows: by two-dimensional drape Cu-TCPP ultrathin nanometer piece point
It is dispersed in the acetone containing iodine, under 30V potential bias, electrophoretic deposition 30s sinks two-dimensional drape Cu-TCPP ultrathin nanometer piece
Product arrives the surface ITO, obtains Cu-TCPP film.
4. all solid state super capacitor of flexibility based on two-dimensional drape metalloporphyrin frame ultrathin nanometer piece as described in claim 1
The preparation method of device, which is characterized in that the preparation step of PPy film are as follows: by paratoluenesulfonic acid sodium salt, p-methyl benzenesulfonic acid monohydrate
It is add to deionized water with pyrroles, after standing 10h, magnetic agitation 10min；Using Ag/AgCl electrode as reference electrode, Pt piece is
To electrode, the ito glass of blank is working electrode, and constant voltage 0.8V carries out electrochemical polymerization, conduction time 600s, system
Standby PPy fexible film out.
5. all solid state super capacitor of flexibility based on two-dimensional drape metalloporphyrin frame ultrathin nanometer piece as described in claim 1
The preparation method of device, which is characterized in that the preparation step of Cu-TCPP/PPy flexible composite film are as follows: by paratoluenesulfonic acid sodium salt, right
Toluenesulfonic acid monohydrate and pyrroles are add to deionized water, after standing 10h, magnetic agitation 10min, with Ag/AgCl electrode
For reference electrode, Pt piece is to electrode, and Cu-TCPP film is working electrode, and constant voltage 0.8V carries out electrochemical polymerization,
Conduction time 600s prepares Cu-TCPP/PPy composite and flexible film.
6. all solid state super capacitor of flexibility based on two-dimensional drape metalloporphyrin frame ultrathin nanometer piece as described in claim 1
The preparation method of device, which is characterized in that H2SO4- PVA hydrogel the preparation method comprises the following steps: being added polyvinyl alcohol into eggplant type bottle,
Ultrapure water is added the concentrated sulfuric acid is added dropwise to above-mentioned solution, reaction flask is sealed after being added dropwise, is transferred under agitation
85 DEG C of oil bath pans react 2h, and solution becomes clear, is cooled to room temperature.
7. all solid state super capacitor of flexibility based on two-dimensional drape metalloporphyrin frame ultrathin nanometer piece as described in claim 1
The preparation method of device, which is characterized in that Cu-TCPP/PPy flexibility all-solid-state supercapacitor the preparation method comprises the following steps: in Cu-
2 drop H are added dropwise in TCPP/PPy composite and flexible electrode surface2SO4- PVA hydrogel, after standing 10min, by another Cu-TCPP/PPy
Composite and flexible electrode is carefully covered on hydrogel surface, stands for 24 hours, sufficiently solidifies to hydrogel, obtains Cu-TCPP/PPy flexibility
All-solid-state supercapacitor.
8. the flexibility according to claim 1 described in any one of -7 based on two-dimensional drape metalloporphyrin frame ultrathin nanometer piece is complete
Application of the solid-state super capacitor in electrochemical energy storage.
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| CN111118533A (en) * | 2020-01-07 | 2020-05-08 | 中国科学院化学研究所 | Preparation method of two-dimensional tetracarboxyphenyl porphyrin metal organic framework film |
| CN114522543A (en) * | 2022-01-19 | 2022-05-24 | 华南理工大学 | Ultrathin two-dimensional Cu-TCPP film and preparation method thereof |
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| CN108550469A (en) * | 2018-04-20 | 2018-09-18 | 南京邮电大学 | A kind of preparation method and application of metalloporphyrin frame/polypyrrole composite and flexible electrode |
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| CN106158429A (en) * | 2016-08-24 | 2016-11-23 | 刘爽 | The method manufacturing graphene-based ultracapacitor |
| CN108538644A (en) * | 2018-03-27 | 2018-09-14 | 南京邮电大学 | A kind of preparation method and application of metalloporphyrin frame/titanium carbide composite and flexible electrode |
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| CN111118533A (en) * | 2020-01-07 | 2020-05-08 | 中国科学院化学研究所 | Preparation method of two-dimensional tetracarboxyphenyl porphyrin metal organic framework film |
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Application publication date: 20190514 |